Phenylene bis (amino substituted benzoate) uv absorbers for polymers

ABSTRACT

ULTRAVIOLET LIGHT ABSORBING COMPOUNDS FOR POLYMERS AND COPOLYMERS ARE DISCLOSED HAVING THE GENERAL FORMULA: WHEREIN   (Y-C6H4)2-Z   R1 IS HYDROGEN OR A LOWER ALKYL GROUP; R2 IS HYDROGEN, A LOWER ALKYL GROUP, AN ACYL GROUP HAVING NOT MORE THAN 20 CARBON ATOMS, A SUBSTITUTED OR NONSUBSTITUTED AROYL GROUP, OR A SUBSTITUTED OR NON-SUBSTITUTED BENZENE SULFONYL GROUP; AND X IS PHENYLENE OR A BIPHENYLENE FRAGMENT HAVING THE FORMULA:   WHEREIN   (R1-N(-R2)-C6H4-COO)2-X   Y REPRESENTS HYDROGEN OR A HALOGEN, AND Z IS A SULFONYL GROUP OR AN ALKYLIDENE GROUP HAVING FROM 3 TO 8 CARBON ATOMS.

United States Patent Office 3,756,983 PHENYLENE BIS(AMlN-SUBSTITUTED BENZO- ATE) UV ABSORBERS FOR POLYMERS Reginoldus Haviuga, Schalkhaar, and Pieter Dirk Swaters,

Lochem, Netherlands, assignors to Koninklijke Industrieele Maatschappij Noury & Van der Lande N.V., Deventer, Netherlands No Drawing. Original application July 8, 1970, Ser. No. 53,315, now Patent No. 3,719,692, dated Mar. 6, 1973. Divided and this application Sept. 14, 1972, Ser. No. 289,055 Claims priority, application Netherlands, July 24, 1969, 6911367 Int. Cl. (1081b 27/68; C08f 45/60; C08g 51/60 U.S. Cl. 26045.85 A 7 Claims ABSTRACT OF THE DISCLOSURE Ultraviolet light absorbing compounds for polymers and copolymers are disclosed having the general formula:

wherein R is hydrogen or a lower alkyl group;

R is hydrogen, a lower alkyl group, an acyl group having not more than carbon atoms, a substituted or nonsubstituted aroyl group, or a substituted or non-substituted benzene sulfonyl group; and

X is phenylene or a biphenylene fragment having the formula:

l 2 wherein Y represents hydrogen or a halogen, and Z is a sulfonyl group or an alkylidene group having from 3 to 8 carbon atoms.

This is a division of application Ser. No. 53,315, filed July 8, 1970, now US. Pat. No. 3,719,692, issued Mar. 6, 1973.

This invention relates to novel ultraviolet light absorbing compounds. The invention also relates to processes for the preparation of said compounds and to new compositions stabilized with the novel compounds,

It is well known that under the influence of ultraviolet light polymers such as polyethylene, polypropylene, polyisobutylene, copolymers of ethylene with higher alkene's such as propylene and butylene or with vinyl acetate, polystyrene, polyvinyl chloride, polyvinylidene chloride, copolymers of vinylchloride with vinylidene chloride, polyvinyl acetate, polyester resins, polyurethanes, cellulose derivatives, etc. may degrade which degradation appears from a deterioration of the mechanical properties and/or from the color of the polymer.

It has now been found, according to the present invention, that this degradation of the polymer may be avoided Patented Sept. 4, 1973 by incorporating in the polymer a stabilizing amount of one or more of the hitherto unknown compounds having the following general formula:

wherein Y is hydrogen or a halogen, and Z is a sulfonyl group or an alkylidene group having from 3 to 8 carbon atoms.

wherein 1 Examples of novel compounds having the structure (I) are mentioned below in Table A:

TABLE A (1) resorcinol di-anthranilate (2) resorcinol bis(N-acetylanthranilate) (3 resorcinol bis(m-N,N-dimethylaminobenzoate) (4) resorcinol bis (N-benzoylanthranilate) (5 resorcinol bis(N (4-tert.butylbenzoyl) anthranilate) (6) resorcinol bis [N- (Z-methoxybenzoyl) anthranilate] (7) 2,2-bis[4-(Z-aminobenzoyloxy)phenylpropane (8 2, Z-bis [4- (Z-N-acetylaminobenzoyloxy) phenyl] propane (9) 2,2-bis [4-(2-N-nonanoylaminobenzoyloxy)phenvll propane 10) bis [4- (Z-aminobenzoyloxy) phenyl] sulfone 1 1 bis [4- (2-N-acetylaminobenzoyloxy) phenyl] sulfone (12) 4-methyl-2,2-bis[4-(Z-aminobenzoyloxy)phenyl] pentanc 13 4-methyl-2,2-bis [4- 2-N-acetylaminobenzoyloxy) phenyl] pentane (14) 2,2-bis[3-chloro-4-(Z-aminobenzoyloxy)phenyl] propane 15 2,2-bis 3-chloro-4- (2-N-acetylaminobenzoyloxy) phenyl1propanc 16) 2,2-bis [4- (4-N-stearoylaminobenzoyloxy)phenyl] propane (17) 2,2-bis[4-(4-aminobenzoyloxy)phenyl] propane l 8 2,2-bis [4- (4-N-tosylaminobenzoyloxy) phenyl] propane 19) 2,2-bis [4- (Z-N-methylaminobenzoyloxy) phenyl] propane 10) 2,2-bis [4- (2-N-methyl-N-acetylaminobenzolyoxy) phenyl]propane benzoyloxy}phenyl] prop ane.

Compounds having the structure (I), wherein R and R represent hydrogen or a lower alkyl group, may be obtained by reacting a compound having the structure wherein R and R represent hydrogen or a lower alkyl group,

and A is halogen or a hydroxyl group, and compounds having the structure (III) or (IV):

OH I

wherein Y is hydrogen or a halogen and Z represents a sulfonyl group or an alkylidene group having from 3 to 8 carbon atoms,

subsequently isolating the resulting compound having respectively the structure (V) or (V1):

and, if desired, converting the same into the corresponding acid amide or sulfonamide.

Compounds according to the present invention with the amino group in the ortho position with respect to the ester carbonyl group may be advantageously obtained by starting from compounds having the structure (VII):

QE-o- (Fig R1 11 (vm 0 o z -{J G 3 I N Y Y N H/ \R1 13/ \R1 (IX) The reaction of the compounds having the structure (II) or (VII) and the compounds having the structure (III) or (IV) is carried out in water or preferably in an organic solvent such as benzene, dioxane, ethylene glycol dimethyl ether, chloroform, carbon tetrachloride, hexane, petroleum ether, and at a temperature between 0 C. and the boiling point of the solvent used and, if desired, in the presence of alkaline compounds such as NaOH, pyridine or triethyl amine.

The compounds having the structures (V), (VI), (VIII) and (IX) may be isolated from the reaction mixture by filtering, decanting and/or distilling off the solvent. After purification by appropriate methods the compounds may be characterized by determining their physical constants such as melting point, refractive index and their characteristic infrared absorption bands.

As reaction components one may use alkylated or nonalkylated isatoic anhydride, alkylated or non-alkylated amino benzoic acid or alkylated or non-alkylated amino benzoyl chloride, bisphenol A, 4-methyl-2,2-bis(4-hydroxyphenyl)pentane, bis(4-hydroxyphenyl)sulfone, 2,2- bis(3-chloro-4-hydroxyphenyl)propane and resorcinol.

The amino benzoyl chlorides to be used may be obtained in a known manner by reacting the corresponding acids with chlorinating agents such as P001 P01 PCl or $001 The conversion of the compounds isolated from the reaction mixture, and having the structures (V), (VI), (VIII) and (IX) into the corresponding acid amides or sulfonamides may be carried out in a dry solvent such as benzene, carbon tetrachloride, chloroform, petroleum ether, hexane, diethyl ether, ethylene glycol dimethyl ether, dioxane, etc., and preferably in the presence of an alkaline substance such as an amine e.g. pyrdine or triethyl amine.

As acylating or sulfonating agents one may use acetyl chloride, n-nonanoyl chloride, stearoyl chloride, benzoyl chloride, substituted benzoyl chloride, p-toluene sulfonyl chloride, p-dodecyl benzene sulfonyl chloride. In addition to acetyl chloride, ketene or acetic acid anhydride may be used as acetylating agent. After purification according to methods well known per se, the acylated or sulfonated compounds may be characterized by determining their physical constants such as melting point or refractive index and their characteristics infrared absorption bands.

The novel compounds according to the present invention may be homogeneously incorporated in the polymers to be stabilized, if desired in the presence of other additives such as plasticizers, pigments, heat stabilizers, lubricants, etc., by well known techniques such as mixing on the roll or calendering. They are incorporated in the polymer preferably in amounts of 0.1-5% by weight.

The following examples and tables further illustrate the invention. Where in these examples and tables reference is made to characteristic infrared absorption bands, these are given in microns.

EXAMPLE I 24.0 g. of isatoic anhydride, 16.2 g. of bisphenol A and 1.42 g. of NaOH were heated in 50 ml. of dioxane for 4.5 hours at 50 C. After cooling, the reaction mixture was poured into water, the precipitate was drawn off by suction, dried and recrystalized with the aid of a mixture of acetone and water in a ratio of 5: 1.

28.3 g. of 2,2-bis[4-(2-aminobenzoyloxy)phenyl]propane were obtained having the structure (X):

C=O ester band: 5.85

Starting from isatoic anhydride and various diphenols the compounds mentioned in the following Tables B and B having the structure (XI) were obtained in an analo- 6 to neutrality and recrystallized from an acetone-water mixture in a ratio of 1:1.

78.0 g. of 2,2-bis[4-(4-aminobenzoyloxy)phenyl]propane were obtained having the structure (XII):

(XII) Yield: 84% NR: 234-242 C. with decomposition Characteristic IR abs. band: 2'87/2'97 gous way: :0 ester band: 5.90

0 x EXAMPLE III A solution of 10.44 g. of 2,2-bis[4-(2-aminobenzoyloxy)phenyl]propane, prepared in the way as described NH: 2 above in Example I, in 125 ml. of chloroform was added TABLE B to a solution of 4.71 g. of acetyl chloride in 75 m1. of dry PWL chloroform. Subsequently the mixture was heated under Diphenol a Solvent (Table A) reflux for 2 hours. After the chloroform had been dis- Resmmol NaOH Dionne (1) tilled off, the residue was re-crystallized from a mixture 4-methy1-2,2-bis(4-hydroxyphenyl) NaOH .-do of chloroform and hexane in a ratio of 1:1. gffigi NaOH (10) 11.8 g. of 2,2 bis [4(2 N acetylaminobenzoyloxy) 2,2-bis(3-chloro-4-hydroxypheuyl) NaOH -.-do pheny1]propane were obtained having the structure propane. (XIII) TABLE B Characteristic Physical constant, IR absorption Product No. (Table A) X 0. bands (1) 13-0011. M.P. 134-136 Nfl as a zsea o=o 8S er (12) 4,4'-(CBH4)QC (0H,) 03.01.1(0113), Resinous product.-- NH 2.8565395 0=o 8S 9! (1o) 4,4'-(o@H|)2s0, M.P. 24mm NH? 2.855526% c=o 8S er (14) 4,4'-(c.H;o1)zo(cH;)= M.P. 191192-....--.. mines/2.98 0=0 ester 5.92.

EXAMPLE II 54.8 g. of p-aminobenzoic acid were heated under reflux with 120 ml. of thionyl chloride for 2 hours and then the excess thionyl chloride was distilled off under reduced pressure. 45.6 g. of bisphenol A were dissolved in absolute ethanol and reacted with 9.2 g. of metallic sodium. After the alcohol had been distilled 0E under reduced pressure,

the dry bis(sodium phenolate) was suspended in 500 ml.

of benzene. A solution of p-amino-benzoyl chloride prepared above in 250 ml. of dry benzene was added to this suspension. The resulting mixture was heated for min utes under nitrogen and under reflux.

After cooling, the precipitate was drawn oif by suction, washed with 4 N sodium hydroxide and then with water Yield: 96% M.P.: 231233 C.

me x111 NH band: 2.95 C=O ester band: 5.80 C=O amide band: 5.90

Starting from compounds described above in Example I and Table B, in an analogous way compounds mentioned in the Tables C and C below, and having the structure (XIV) were obtained in the presence or absence of an alkaline substance.

Characteristic IR abs.

TABLE Characteristic IR absorptions Product N o. of Physical N H C=O ester 0:0 amide Table A R; X constant, C. band band band (2) COOH; 1,3-CaH M.P. 176-179 3. 00 6. 89 5. 92 (4) CO CaHs 1,3-C0H4 M.P. 186-189. 2. 99 5. 90 6. 00 (5) 000mm (CHQa-p 1,3-CtH4 M.P. 203-207- 2. 99 5. 99 5. 99 (6) CO CeH4 3-0 ,3-CuH4 M.P. 189-193 3. 02 6. 84 6. 02 (9) CO CaHn-n 4,4-(CtH4)zC (CH Liquid nu 1.4962-. 2. 93 6. 75 6. 85 (ll) COCH; 4,4-(C5H4)2SO2 M.P. 142-143 2. 98 5. 88 5. 91 (13).- COCHZ 4,4(CsH4)zC (CH3) CHzCH (CH3): Reslnous product--. 3. 00 5. 90 5. 92 (15) COCH; 4,4'-(CeH3Cl)zC(CH3)z M.P. 216-219 3.00 5.82 5.92

EXAMPLE IV EXAMPLE VI 2,2 bis[4 (2 N acetylaminobenzoyloxy)phenyl] propane having the structure (XIII) was also obtained by passing ketene into a solution of g. of the corresponding diamine in 200 m1. of n-butyl acetate at 50 C. (for 20 minutes. After the precipitate formed had been worked up in the way as described above in Example III, the endproduct was obtained in a yield of 5.19 g. of 2,2 bis[4 (2 N methylaminobenzoyloxy) When acetylated with acetic anhydride in boiling ed 1h t t benzene, the end-product was obtained inayield of 70%. ga 2 we were ab am having 6 S rue um 15 5.31 g. of N-methyl isatoic anhydride, 3.42 g. of bisphenol A and 0.30 g. of pulverulent NaOI-I were heated in 50 ml. of dioxane for 8 hours at 100 C. After cooling, the reaction mixture was poured into hexane. The precipitate formed was drawn off by suction and subsequently 20 dried.

EXAMPLE V 0 0 0 11.65 g. of 2,2 bis [4 (4 aminobenzoyloxy)phenyl] ii-O-Q--Q-O-ii propane obtained in the way described above in Example i II, and 6 g. of pyridine were dissolved in 100 ml. of NH HN ethylene glycol dimethyl ether. 9.5 g. of p-toluene sul- 6 fonyl chloride in 50 ml. of ethylene glycol dimethyl ether (XVII) added to this solution and then the reaction mixture was heated under reflux for 3.5 hours. After cooling the mix- Yi ld; 82%

ture, the solvent was distilled 01f under reduced pressure. 11; 37 192 C The residue was washed with 4 N hydrochloric acid and NH band: 2.92

then with water to neutrality and subsequently dried. By character IR {C=O ester band: 5.93 recrystallization from a mixture of chloroform and petroleum ether in a ratio of 1:1,14.1 g. of 2,2-bis[4-(4-N- EXAMPLE VII tosylaminobenzoyloxy) phenyl] propane were obtained 1.10 g. of acetyl chloride dissolved in chloroform were having the structure (XV): added to 2.47 g. of 2,2-bis[4-(Z-N-methylaminobenzoyl- 0 (His 0 O with decomposition 0xy)phenyl] propane, obtained in the way described above H band. 305 in Example VI, dissolved in 30 ml. of chloroform. The Ch i i 1R b 0:0 ester b d; 530 mixture was then heated under reflux for 2 hours. After {:=O band: 7.53/8.64/ 10.95 the chloroform had been distilled off, the residue was re- Starting from 2,2 bis[4-(4-aminobenzoyl0xy)phenyl] crystallized from a mixture of acetone and water in a propane obtained in the way described above in Example ratio f II, in an analogous way the compounds mentioned in the following Tables D and D' having the structure (XVI) of 1mm (2 N methyl N acetylammobenzoyl were obtained in the presence or absence of an alkaline oxwphenynpropane were obtained having the Structure substance. (XVIII):

Q- Q -Q (XVI) 0 OH 0 TABLE 1) g a g Q Pagans? CH H CH 0.0 Aoyletlng agent Solvent Base TahleA N N Stearoyl chloride Dloxane (16) p-Dodecylbenzenesulfonyl Ethylene lycol Pyridine (21) 011, CHCO chloride. dimethy ether. (XVIII) TABLE D' lrilmduet Ph 1 lconst t s ca an T31 322: 0 R1 C Characteristic IR absorption 16 000 H -n M.P. -160 NH band 2.97 C=O ester band 5.82 C=O amide band 5.90. E21; sozclhibwnzt-p Reslnous product.-." NH bend 3.05} c=o ester band 5.80} s=0 band yam 10.95.

9 Yield: 72% M.P.: l28132 C. Characteristic IR abs.: C=O ester band 6.08

EXAMPLE VIII 33.0 g. of m-N,N-dimethyl aminobenzoic acid were heated under nitrogen with 60 g. of thionyl chloride for 3 hours at 50 C. After the excess thionyl chloride had been distilled off under reduced pressure, the residue was decolorized in a solution of chloroform with the aid of conventional absorption carbon. After the chloroform had been distilled off, 35.5 g. of m-N-N-dimethyl aminobenzoyl chloride were obtained.

7.32 g. of the product thus obtained, 2.20 g. of resorcinol and 4.8 ml. of pyridine were heated under nitrogen in 100 ml. of chloroform for 4 /2 hours at 60 C. After the mixture had been washed with 4 N hydrochloric acid and water to neutrality, the chloroform was dried and then the solvent was distilled off.

5.24 g. of resorcinol bis(m-N,N-dimethyl aminobenzoate) were obtained having the structure (XIX):

N E3 \CHQ on. 0113 (XIX) Yield: n =L5667 Characteristic IR abs.: C=O ester band 5.82

EXAMPLE IX 100 g. of polyvinylchloride, 35 g. of dioctyl phthalate, 2 g. of bariumcadmium stabilizer (Estabex BC-148) and 200 mg. of 2,2 bis[4 (2-N-acetylaminobenzoyloxy) phenylJpropane were mixed on a roll at 180 C. until a homogeneous, colorless, transparent sheet was obtained. This sheet was pressed to a uniform thickness of 0.2 mm. Subsequently it was subjected to ultraviolet radiation in a Xenotester for 2000 hours. Next, the degradation was determined visually and rated according to a numerical scale ranging from 0 to 6, wherein the value 0 indicates that no degradation had taken place.

In an analogous way, the stabilizing power of other compounds according to the present invention was determined. The compounds used and the degradation as measured are listed below in Table E:

TABLE E EXAMPLE X 100 g. of high-density polyethylene were mixed with 250 mg. of 2,2-bis[4-(4 N stearoylaminobenzoyl)phenyl]propane and worked on a roll into a colorless, transparent sheet at a temperature of 120 C. This sheet was pressed to a uniform thickness of 0.2 mm. and subsequently subjected to ultraviolet radiation in Xenotester for 2000 hours. As a measure of the degradation of the 10 sheet the carbonyl content was determined. This content was 0.21. A nonstabilized sheet irridated in an analogous Way had a carbonyl content of 0.40.

What is claimed is:

1. A composition of matter comprising a polymer selected from the group consisting of polyethylene, polypropylene, polyisobutylene, copolymers of ethylene with higher alkenes or with vinyl acetate, polystyrene, polyvinylchloride, polyvinylidene chloride, copolymers of vinyl chloride with vinylidene chloride, polyvinylacetate, polyester resins, polyurethanes and cellulose resins and an ultraviolet light absorbing compound or mixture of compounds having the formula I 2 wherein R is hydrogen or a methyl group,

R is hydrogen, a methyl group, an alkanoyl group having not more than 20 carbon atoms, an unsubstituted or substituted benzoyl group having a substituent selected from an alkyl group having 1-6 carbon atoms, a methoxy group and a chloro atom, an unsubstituted benzene sulphonyl or benzene sulphonyl group substituted by an alkyl group having 1-12 carbon atoms, and

X is phenylene or a biphenyl fragment having the formula wherein Y represents hydrogen or chloro, and Z is a sulphonyl group or an alkylidene group having from 3 to 8 carbon atoms.

2. The composition of matter of claim 1 wherein the ultraviolet light absorbing compound is present in an amount of about 0.15% by weight of the polymer.

3. The composition of matter of claim 1 wherein the polymer is polyvinyl chloride or high-density polyethylene.

4. Shaped articles when obtained from the compositions defined in claim 1.

5. The composition of matter of claim 1 wherein said light absorbing compound is resorcinol bis(N-benzoylanthranilate) 6. The composition of matter of claim 1 wherein said light absorbing compound is resorcinol bis[N-(4-tert.- butylbenzoyl) anthranilate] 7. The composition of matter of claim 1 wherein said light absorbing compound is resorcinol bis[N-(2-methoxybenzoyl) anthranilate] References Cited UNITED STATES PATENTS 3,022,268 '2/ 1962 Armitage et al 260-4585 3,069,456 12/1962 Strobel et al. 260-45.85

DONALD E. CZAJA, Primary Examiner V. P. HOKE, Assistant Examiner US. Cl. X.R. l06-178, 179 

